Amorphous nickel-free zirconium alloy

ABSTRACT

An amorphous Nickel-Free Zirconium alloy which is readily formed through copper mold casting, comprising a composition consisting of four elements in which the first element is Zr, the second element is Ti, the third element is Cu and the fourth element is Al, wherein an atomic percent of the first to the fourth elements in the composition are represented by a, b, c and d respectively, wherein a=45˜69%, b=0.25˜8%, c=21˜35%, and d=7.5˜15%, where a sum of a, b, c and d is smaller than or equal to 100%. The composition of the amorphous alloy within the above range is melted in a copper mold to form bulk amorphous materials or parts which have characteristics of high tensile strength, high fracture toughness, low Young&#39;s modulus and high corrosion resistance.

BACKGROUND OF THE PRESENT INVENTION

1. Field of Invention

The present invention relates to an amorphous alloy (or metallic glass), and more particularly to an amorphous nickel-free zirconium alloy which is readily formed through copper mold casting.

2. Description of Related Arts

Compared to general polycrystalline structured materials, amorphous alloy (also known as metallic glass) has the major structural features of absence of long-range order and grain-boundary. Accordingly, amorphous alloy is advantageous in providing high strength level, high resistance to corrosion and isotropic feature and has great potentials in a variety of applications in the field of micromechanics, microelectronics, sports apparatus or equipment, sophisticated equipment, security device and medical materials, etc. In comparison, general metals and alloys undergo crystallization when normally cooled from liquid state to form polycrystalline structured materials, while amorphous alloys are usually cooled below its glass transition temperature (which is usually represented by T_(g)) from the alloy melt in order to avoid obvious crystallization such that the alloy melt is frozen into structurally amorphous (glass state) metallic materials.

Since the 60's in the 20 century, people discovered that certain alloys, if cooled at sufficiently high cooling rate, is capable of being under-cooled (in which crystallization does not happen below its melting point), and remaining in a highly viscous liquid state or glass state. The typical cooling rate requirement is about 10⁴ K/s to 10⁶ K/s. In order to achieve this high cooling rate, a small amount of the alloy melt is required to contact with a thermally conductive substrate (such as copper plate) which is maintained under room temperature. This limiting factor is due to the requirement of sufficiently high rate of heat absorption from the alloy melt in order to suppress the crystallization process. Accordingly, during the early development, the majority of amorphous alloys is limited to the forms of powder, thin foil, wires and ribbons, etc, which are formed and obtained through spraying the alloy melt onto a cooling copper wheel which is rotated at high speed, dripping the alloy melt between cooling hammer bulk, or moving the cooling substrate at high speed to penetrate through a narrow nozzle, etc.

The ability of alloy melt to resist crystallization during cooling refers to the critical cooling rate required for forming amorphous alloy from the alloy melt. In order to extend the manufacture or application, the ideal cooling rate is equal to or lower than 10⁻¹˜10² K/sec so as to inhibit crystallization. The critical cooling rate of forming amorphous alloy from alloy melt is approximately inversely proportional to a square of the geometry of a bulk material, which is R_(c)=10/t², where R_(c) is the critical cooling rate (unit: K/s) and t is the thickness (unit: centimeter). If R_(c) decreases, t will increase. If the critical cooling rate of the alloy decreases, amorphous alloy materials or parts with greater cross-sectional area can be fabricated. In the 90's of the 20 century, people discover that alloys including the Zirconium, Palladium, Platinium, Yttrium, Calcium, Iron, Copper, Lanthanum, Neodymium or Magnesium based are capable of forming bulk amorphous alloys with a thickness or diameter at centimeter level through copper mold casting. The critical cooling rate for forming the glass state of each of the above amorphous alloys is lower than 10 K/sec.

Usually, the glass-forming ability of an alloy and the thermal stability of supercooled liquid mainly depends on the chemical composition of the alloy, and are highly sensitive to variation in the chemical composition. Under some circumstances, even a change of an element content of 1% (in atomic percent) may cause dramatic effect to the ability of formation of amorphous form. The composition of alloy which is complicated appropriately (i.e., formed by a plurality of alloy elements) can improve the glass-forming ability of the alloy and decrease the critical cooling rate for forming the glass state alloy. In view of Zirconium-based alloys, there exists binary alloy of Zr—Cu, ternary alloy of Zr-TM-Al (TM refers to Cu, Ni or Co) and Zr-TM-Be, quaternary alloy of Zr—Cu—Ni—Al, quinary alloy of Zr—Ti—Cu—Ni—Be which is capable of forming bulk amorphous materials from its corresponding alloy melt by cooling within certain specific composition range. Amorphous alloys of different compositions have a wide range of critical cooling rate, which is ranged from 10⁶ K/s to 10 K/s. Zirconium based alloy which is of ternary or higher level has a significantly lower critical cooling rate than that of the Zirconium based alloy with binary or lower order, and has a greater glass-forming ability. For example, with copper mold casting, Zr₅₇Ti₅Cu₂₀Ni₈Al₁₀ (subscript refers to atomic percentage) alloy can form glassy rods with a diameter of 15 mm.

Compared with their polycrystalline counterparts, amorphous zirconium alloy exhibits high yield strength, high elastic limit, low Young's modulus, high corrosion resistance and good wear resistance. Zirconium based alloy with high glass-forming ability can be fabricated in the form of rod, plate or a particular parts with larger size through direct casting to meet a variety of application requirements. In particular, it is possible to develop for use in biomedical device or implants. The properties of amorphous zirconium alloy make it superior to conventional metallic materials such as stainless steel, Cobalt-Chromium alloy, titanium or titanium alloy and NiTi shape memory alloy for biomedical implants. When compared to conventional metallic biomedical materials, amorphous zirconium alloy has characteristics of extremely high strength which is capable of reaching a yield strength of 1500˜2000 megapascals; relative higher specific strength; high elastic limit (˜2%). Also, amorphous zirconium alloy has superior corrosion resistance and good wear resistance, and is compatible to magnetic resonance imaging and has lower magnetic susceptibility.

However, currently available zirconium based amorphous alloys normally contain toxic elements such as nickel and beryllium so as to ensure robust glass-forming ability. Removing the toxic elements such as nickel and beryllium in zirconium based alloy is a prerequisite of biomedical application. There is a need of a zirconium based alloy without toxic elements such as nickel and beryllium.

SUMMARY OF THE PRESENT INVENTION

An object of the present invention is to provide an amorphous zirconium alloy which is readily formed, wherein the zirconium alloy does not contain nickel element and can be made through copper mold casting process to form an bulk amorphous material or a part of a device having a size at least 1 millimeter which has characteristics of high strength, high fracture toughness, and high resistance to corrosion under human biological environment.

Additional advantages and features of the invention will become apparent from the description which follows, and may be realized by means of the instrumentalities and combinations particularly pointed out in the appended claims.

According to the present invention, the foregoing and other objects and advantages are attained by an amorphous Nickel-Free Zirconium alloy which is readily formed through copper mold casting, comprising a composition consisting of four elements in which the first element is Zr, the second element is Ti, the third element is Cu and the fourth element is Al, wherein an atomic percent of the first to the fourth elements in the composition are represented by a, b, c and d respectively, wherein a=45˜69%, b=0.25˜8%, c=21˜35%, and d=7.5˜15%, where a sum of a, b, c and d is smaller than or equal to 100%. In the actual application, Zr can be partially substituted by Hf or Nb.

In the amorphous Nickel-Free Zirconium alloy which is readily formed through copper mold casting according to the preferred embodiment of the present invention, the followings are preferred.

The composition has a chemical formula of Zr_(a)Ti_(b)Cu_(c)Al_(d) in which a+b has a range of 55˜69%.

An atomic percentage of Zr relative to Ti is 92˜99.5%, wherein an atomic percentage of Ti relative to Zr is 0.5˜8%.

Preferably, in the chemical formula, a+b has a range of 55˜69% in atomic percent, and Al has a range of 8˜13% in atomic percent, thereby the alloy has a high formation ability of amorphous alloy (for example, amorphous rod with a diameter of 10 mm can be formed), while having good mechanical properties. The nickel-free zirconium alloy according to the preferred embodiment of the present invention has a tensile strength of 1500˜1700 MPa, a Young's modulus of 80-90 GPa, density of 6.0-7.0 g/cm³, and is suitable for use in orthopedic fixation device and casing for timepiece or cell phone.

Accordingly to a preferred embodiment of the amorphous Nickel-Free Zirconium alloy which is readily formed through copper mold casting of the present invention, the composition further consists a fifth element Hf and has a chemical formula of Zr_(a)Hf_(e)Ti_(b)Cu_(c)Al_(d), where a, b, c, d, e are atomic percent of the first to fifth elements respectively, wherein a=45˜69%, b=0.25˜8%, c=21˜35%, d=7.5˜15%, b+e=0.25˜15%, where a sum of a, b, c, d and e is equal to 100%.

In addition, in the amorphous Nickel-Free Zirconium alloy which is readily formed through copper mold casting according to the preferred embodiment of the present invention, the followings are preferred.

In said chemical formula of said composition of Zr_(a)Hf_(e)Ti_(b)Cu_(c)Al_(d), a+b+e has a range of 55˜69%.

An atomic percentage of Zr relative to Ti is 92˜99.5%, wherein an atomic percentage of Ti relative to Zr is 0.5˜8%, thereby the alloy has a high glass-forming ability (for example, amorphous rod with a diameter of 10 mm can be formed), while having good mechanical properties. The nickel-free zirconium alloy according to this preferred embodiment of the present invention has a tensile strength of 1500˜1700 MPa, a Young's modulus of 80-90 GPa, a density of 6.0-7.0 g/cm³, and is suitable for use in orthopedic fixation device and casing for timepiece or cell phone.

Accordingly to another preferred embodiment of the amorphous Nickel-Free Zirconium alloy which is readily formed through copper mold casting of the present invention, the composition further consists an additional element Nb and has a chemical formula of Zr_(a)Nb_(f)Ti_(b)Cu_(c)Al_(d), where a, b, c, d, f are atomic percents of the first to fourth elements and the additional element respectively, wherein a=45˜69%, b=0.25˜8%, c=21˜35%, d=7.5˜13%, b+0.25˜10%, where a sum of a, b, c, d and f is equal to 100%.

In addition, in the amorphous Nickel-Free Zirconium alloy which is readily formed through copper mold casting according to the preferred embodiment of the present invention, the followings are preferred.

In said chemical formula of said composition of Zr_(a)Nb_(f)Ti_(b)Cu_(c)Al_(d), a+b+f has a range of 55˜69%.

An atomic percentage of Zr relative to Ti is 92˜99.5%, wherein an atomic percentage of Ti relative to Zr is 0.5˜8%. The nickel-free zirconium alloy according to this preferred embodiment of the present invention has a tensile strength of 1500˜1700 MPa, a Young's modulus of 80-90 GPa, a density of 6.0-7.0 g/cm³, and is suitable for use in orthopedic fixation device and casing for timepiece or cell phone.

The multi-component of zirconium alloy according to the preferred embodiment of the present invention has a very good glass-forming ability which can be prepared through copper mold casting to form bulk materials in amorphous state. The size and geometry of as-cast material depends on the inner cavity of the copper mold, which can be in a shape of rod, prism, thin plate or polyhedron. If the inner cavity is in the shape of cylinder, the critical thickness (or diameter) for forming bulk amorphous alloy is at least 1 mm. The bulk amorphous alloy refers to a bulk material in which at least 50% of the material is in glassy state or containing at least 50% of amorphous phase. Usually, the percentage of amorphous phase is basically 95% according to the preferred embodiment of the present invention. Different alloy composition may have different critical thickness for forming the bulk amorphous material.

In order to ensure the glass-forming ability and mechanical properties, the amorphous alloy according to the preferred embodiment of the present invention includes a total alloy content of “Zr+Ti+Hf+Nb” which is not less than 55% (in atomic percent), while not exceeding approximately 69% (in atomic percent). If the total alloy content of “Zr+Ti+Hf+Nb” falls outside the above range, the glass-forming ability will be degraded. Accordingly, the amorphous alloy cannot be obtained at a relatively lower cooling rate, and the monolithic amorphous alloy material or parts which have a thickness of at least 1mm cannot be produced. In order to ensure the formation of amorphous phase from cooling the alloy melt, the total content of Cu in the alloy cannot be lower than 21% (in atomic percent) or higher than 35% (in atomic percent). Otherwise, during the cooling process, intermetallics would be formed instead of the monolithic amorphous structure. The Al element in the alloy strongly influences the glass-forming ability and mechanical properties, and its content cannot be lower than 7.5% (in atomic percent) or higher than 15% (in atomic percent). (In ZrTiNbCuAl series, not more than 13% (in atomic percent)).

The multi-component amorphous zirconium alloy according to the preferred embodiment of the present invention allows the existence of a small quantity of impurities such as hydrogen, oxygen, nitrogen, carbon and phosphorus elements which are originated from the starting materials, the atmosphere during the melting and casting process, or from the crucible materials. The glass-forming ability of zirconium based alloy is very sensitive to impurities. Even a small amount of impurities will significantly degrade the glass-forming ability. The major elements Zr, Ti, and Hf of the alloy composition have strong affinity to impurities in gaseous state such as oxygen, and the glass-forming ability will be decreased. Therefore, impurities should be avoided during processing of the amorphous alloy, for example, the oxygen content in the alloy should not be more than 0.1% (in percentage weight).

The multi-component amorphous zirconium alloy according to the preferred embodiment of the present invention basically includes the following steps for fabrication: Starting materials of pure Zr, Cu, Al, Ti, Hf, Nb elements with purity better than 99.5 wt. % are provided in accordance to the chemical composition as desired The master alloy ingots with the nominal composition (in at. %) are prepared by arc melting under a Ti-gettered argon atmosphere in a water-cooled copper hearth. The alloy ingots are re-melted several times to ensure compositional homogeneity. Then, the master alloy was re-melted by arc melting or induction melting. After that, by differential pressure or gravity, the required plate or rod shaped bulk materials or other parts of irregular shapes are fabricated by using vacuum suction casting or copper mold casting of the arc-melted alloys. Also, the melted master alloy can be cast to near-net shape parts such as casing for timepiece or cell phone etc.

According to the heat thermal conductivity between the copper mold and the alloy melt, the centered portion of thin plate or rod has the lowest cooling rate and the surface which is in direct contact with the copper mold has the highest cooling rate. Therefore, the possibility of forming a monolithic amorphous structure of the bulk alloy is restricted by the cooling rate at the centered portion. One order of increment of thickness (or diameter) of the bulk material requires approximately two order of decrement of the critical cooling rate for forming the amorphous alloy. For example, for a fully amorphous rod having a diameter of approximately 1 mm and 10 mm, the critical cooling rate is equal to 500 K/s and 10 K/s respectively. Many conventional processing techniques can achieve such level of cooling rate. For example, the alloy melt can be cast into a water-cooled copper mold to produce an amorphous materials in bulk, plate, rod form or parts of near net-shape with a thickness of more than 1 mm.

According to the amorphous alloy of the present invention, the critical cooling rate (which is the minimum cooling rate required to avoid crystallization during cooling) is approximately 500˜10 K per second, therefore producing process such as normal copper mold casting can be used to produce amorphous materials which are bulk-shaped, plate-shaped, and rod-shaped or are in a particular shape for parts. The master alloy can also be placed in a quartz crucible which does not chemically react with the master alloy and melted until compositional homogeneity after vacuum sealing the quartz crucible. Then, the crucible is quenched in water (or in other quenching media such as saline water) to obtain the amorphous materials.

Still further objects and advantages will become apparent from a consideration of the ensuing description and drawings.

These and other objectives, features, and advantages of the present invention will become apparent from the following detailed description, the accompanying drawings, and the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention is further described in details with the following drawings.

FIG. 1 is a composition map of amorphous alloy formation. As-cast rods with a diameter larger than 1mm in this composition region are obtained through a fixed content of zirconium and titanium, and a variation of copper and aluminum content when the atomic percentage of zirconium and titanium are 99.4% and 0.6% respectively according to a preferred embodiment of the present invention.

FIG. 2 is a composition map of amorphous alloy formation. As-cast rods with a diameter larger than 1 mm in this composition region are obtained through a fixed content of zirconium and titanium, and a variation of copper and aluminum content when the atomic percentage of zirconium and titanium are 92% and 8% respectively according to a preferred embodiment of the present invention.

FIG. 3 is a composition map of amorphous alloy formation. As-cast rods with a diameter larger than 1mm in this composition region are obtained through a fixed content of zirconium, titanium, and hafnium with a variation of copper and aluminum content when the relative atomic percentage of zirconium and titanium are 92% and 8% respectively and the relative atomic percentage of the total content of Zr and Ti and the atomic percentage of Hf are 92% and 8% respectively according to a preferred embodiment of the present invention.

FIG. 4 is a composition map of amorphous alloy formation. As-cast rods with a diameter larger than 1 mm in this composition region are obtained through a fixed content of zirconium, titanium and niobium, and a variation of copper and aluminum content when the relative atomic percentage of zirconium and titanium are 92% and 8% respectively and the relative atomic percentage of a total content of zirconium and titanium, and the atomic percentage of niobium are 98% and 2% respectively according to a preferred embodiment of the present invention.

FIG. 5 is an illustration of X-ray diffraction patterns for the cross-section of as-cast rods from four representative alloys through which the alloy structure is proved to be a fully amorphous structure, where curve a, b, c, d is corresponding to rods with a preset diameter and alloy composition as follows:

a: Zr_(60.9)Ti_(2.1)Cu₂₅Al₁₂, diameter: 10 mm (see exemplary embodiment 1);

b: Zr_(61.6)Ti_(4.4)Cu₂₄Al₁₀, diameter: 8 mm (see exemplary embodiment 2);

c: Zr_(58.46)Ti_(2.02)Hf_(2.52)Cu₂₅Al₁₂, diameter: 10 mm (see exemplary embodiment 3);

d: Zr_(59.68)Ti_(2.06)Nb_(1.26)Cu₂₅Al₁₂, diameter: 10 mm (see exemplary embodiment 4).

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Exemplary Embodiment 1: Zr_(60.9)Ti_(2.1)Cu₂₅Al₁₂ Alloy (Numeric References Refer to Atomic Percentage)

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 55 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, turning the copper crucible to pour the alloy melt to a copper mold for casting. The copper mold has an inner cavity with a preset size of φ10 mm×110 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 10 mm and a length of 70 mm. The cross-section of the alloy rod is polished and used for X-ray diffraction (XRD) analysis. A broad diffusive diffraction pattern which is characteristic of an amorphous structure with no evidence of any crystalline peaks indicates the entire alloy rod is fully amorphous, which is shown in curve ‘a’ of FIG. 5.

Exemplary Embodiment 2: Zr_(61.6)Ti_(4.4)Cu₂₄Al₁₀ Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 40 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, turning the copper crucible to pour the alloy melt to a copper mold for casting. The copper mold has an inner cavity with a preset size of φ8 mm×110 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 8 mm and a length of 70 mm. The cross-section of the alloy rod is polished and used for X-ray diffraction (XRD) analysis. A broad diffusive diffraction pattern which is characteristic of an amorphous structure with no evidence of any crystalline peaks indicates the entire alloy rod is fully amorphous, which is shown in curve ‘b’ of FIG. 5.

Exemplary Embodiment 3: Zr_(58.46)Ti_(2.02)Hf_(2.52)Cu₂₅Al₁₂ Alloy

The starting materials are pure Zr, Ti, Cu, Al, Hf in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quinary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 55 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, turning the copper crucible to pour the alloy melt to a copper mold for casting. The copper mold has an inner cavity with a preset size of φ10 mm×110 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 10 mm and a length of 70 mm. The cross-section of the alloy rod is polished and used for X-ray diffraction (XRD) analysis. A broad diffusive diffraction pattern which is characteristic of an amorphous structure with no evidence of any crystalline peaks indicates the entire alloy rod is fully amorphous, which is shown in curve ‘c’ of FIG. 5.

Exemplary Embodiment 4: Zr_(59.68)Ti_(2.06)Nb_(1.26)Cu₂₅Al₁₂ Alloy

The starting materials are pure Zr, Ti, Cu, Al, Nb in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quinary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 55 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, turning the copper crucible to pour the alloy melt to a copper mold for casting. The copper mold has an inner cavity with a preset size of φ10 mm×110 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 10 mm and a length of 70 mm. The cross-section of the alloy rod is polished and used for X-ray diffraction (XRD) analysis. A broad diffusive diffraction pattern which is characteristic of an amorphous structure with no evidence of any crystalline peaks indicates the entire alloy rod is fully amorphous, which is shown in curve ‘d’ of FIG. 5.

Exemplary Embodiment 5: Zr_(62.53)Ti_(4.47)Cu₂₃Al₁₀ Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 3.5 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, promptly increasing a current such that the viscosity of the alloy melt is decreased and the alloy melt is sucked into the inner cavity of the copper mold by gravity. Otherwise, an appropriate level of pressure difference is added between the electric arc furnace and the copper mold atmosphere such that the alloy melt is suck into the copper mold by pressure. The copper mold has an inner cavity with a preset size of φ4 mm×32 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 4 mm and a length of 30 mm.

Exemplary Embodiment 6: Zr_(62.53)Ti_(4.47)Cu₂₄Al₉ Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 20 g master alloy ingot in a quartz tube which has a nozzle with a diameter of 0.5 at a bottom end of the quartz tube. The quartz tube with the master alloy ingot is placed inside an induction coil of the induction melting unit. A copper mold which has an inner cavity with a preset of φ8 mm×100 mm is placed right below the bottom of the quartz tube. The induction melting unit, through suction provided by a mechanical pump and a diffuse pump, is set to vacuum level at 10−3 Pa. Then, highly purified hydrogen gas at 0.03 MPa is injected into the induction melting unit. The master alloy ingot is heated inside the induction coil until the master alloy ingot is completely melted into an alloy melt. Highly purified hydrogen gas is injected into the quartz tube at a top end thereof such that the alloy melt is injected into the inner cavity of the copper mold (other dimension with different diameter and length or various geometry can also be selected) at the bottom portion of the quartz tube. After cooling, the alloy melt forms an amorphous material of alloy rod which has a size of φ8 mm×40 mm.

Exemplary Embodiment 7: Zr_(46.7)Ti_(2.3)Cu₂₁Al₁₀ Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 0.5 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, promptly increasing a current such that the viscosity of the alloy melt is decreased and the alloy melt is sucked into the inner cavity of the copper mold by gravity. Otherwise, an appropriate level of pressure difference is added between the electric arc furnace and the copper mold atmosphere such that the alloy melt is suck into the copper mold by pressure. The copper mold has an inner cavity with a preset size of φ1 mm×32 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 1 mm and a length of 30 mm.

Exemplary Embodiment 8: Zr_(61.87)Ti_(2.13)Cu₂₅Al₁₁ Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 55 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, turning the copper crucible to pour the alloy melt to a copper mold for casting. The copper mold has an inner cavity with a preset size of φ10 mm×110 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 10 mm and a length of 70 mm.

Exemplary Embodiment 9: Zr_(55.7)Ti_(0.3)Cu₂₅Al₁₀Nb₉ Alloy

The starting materials are pure Zr, Ti, Cu, Al, Nb in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quinary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 0.5 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, promptly increasing a current such that the viscosity of the alloy melt is decreased and the alloy melt is sucked into the inner cavity of the copper mold by gravity. Otherwise, an appropriate level of pressure difference is added between the electric arc furnace and the copper mold atmosphere such that the alloy melt is suck into the copper mold by pressure. The copper mold has an inner cavity with a preset size of φ1 mm×32 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 1 mm and a length of 30 mm.

Exemplary Embodiment 10: Zr_(62.53)Ti_(4.47)Cu₂₅Al₈ Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 2 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, promptly increasing a current such that the viscosity of the alloy melt is decreased and the alloy melt is sucked into the inner cavity of the copper mold by gravity. Otherwise, an appropriate level of pressure difference is added between the electric arc furnace and the copper mold atmosphere such that the alloy melt is suck into the copper mold by pressure. The copper mold has an inner cavity with a preset size of φ3 mm×32 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 3 mm and a length of 30 mm.

Exemplary Embodiment 11: Zr₅₈Ti₂Cu₂₈Al₁₂ Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 20 g master alloy ingot in a quartz tube which has a nozzle with a diameter of 0.5 at a bottom end of the quartz tube. The quartz tube with the master alloy ingot is placed inside an induction coil of the induction melting unit. A copper mold which has an inner cavity with a preset of φ8 mm×100 mm is placed right below the bottom of the quartz tube. The induction melting unit, through suction provided by a mechanical pump and a diffuse pump, is set to vacuum level at 10−3 Pa. Then, highly purified hydrogen gas at 0.03 MPa is injected into the induction melting unit. The master alloy ingot is heated inside the induction coil until the master alloy ingot is completely melted into an alloy melt. Highly purified hydrogen gas is injected into the quartz tube at a top end thereof such that the alloy melt is injected into the inner cavity of the copper mold (other dimension with different diameter and length or various geometry can also be selected) at the bottom portion of the quartz tube. After cooling, the alloy melt forms an amorphous material of alloy rod which has a size of φ8 mm×40 mm.

Exemplary Embodiment 12: Zr_(62.83)Ti_(2.17)Cu₂₄Al₁₁ Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 55 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, turning the copper crucible to pour the alloy melt to a copper mold for casting. The copper mold has an inner cavity with a preset size of φ10 mm×110 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 10 mm and a length of 70 mm.

Exemplary Embodiment 13: Zr_(61.87)Ti_(2.13)Cu₂₃Al₁₃ Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 55 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, turning the copper crucible to pour the alloy melt to a copper mold for casting. The copper mold has an inner cavity with a preset size of φ10 mm×110 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 10 mm and a length of 70 mm.

Exemplary Embodiment 14: Zr_(64.77)Ti_(2.23)Cu₂₂Al₁₁ Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 3.5 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, promptly increasing a current such that the viscosity of the alloy melt is decreased and the alloy melt is sucked into the inner cavity of the copper mold by gravity. Otherwise, an appropriate level of pressure difference is added between the electric arc furnace and the copper mold atmosphere such that the alloy melt is suck into the copper mold by pressure. The copper mold has an inner cavity with a preset size of φ4 mm×32 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 4 mm and a length of 30 mm.

Exemplary Embodiment 15: Zr_(61.87)Ti_(2.13)Cu₂₆Al₁₀ Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 55 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, turning the copper crucible to pour the alloy melt to a copper mold for casting. The copper mold has an inner cavity with a preset size of φ10 mm×110 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 10 mm and a length of 70 mm.

Exemplary Embodiment 16: Zr_(58.97)Ti_(2.03)Cu₂₈Al₁₁ Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 3.5 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, promptly increasing a current such that the viscosity of the alloy melt is decreased and the alloy melt is sucked into the inner cavity of the copper mold by gravity. Otherwise, an appropriate level of pressure difference is added between the electric arc furnace and the copper mold atmosphere such that the alloy melt is suck into the copper mold by pressure. The copper mold has an inner cavity with a preset size of φ4 mm×32 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 4 mm and a length of 30 mm.

Exemplary Embodiment 17: Zr_(52.9)Ti_(4.6)Cu₃₅Al_(7.5) Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 0.5 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, promptly increasing a current such that the viscosity of the alloy melt is decreased and the alloy melt is sucked into the inner cavity of the copper mold by gravity. Otherwise, an appropriate level of pressure difference is added between the electric arc furnace and the copper mold atmosphere such that the alloy melt is suck into the copper mold by pressure. The copper mold has an inner cavity with a preset size of φ1 mm×32 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 1 mm and a length of 30 mm.

Exemplary Embodiment 18: Zr_(50.7)Ti_(0.3)Cu₂₅Al₁₀Hf₁₄ Alloy

The starting materials are pure Zr, Ti, Cu, Al, Hf in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quinary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 0.5 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, promptly increasing a current such that the viscosity of the alloy melt is decreased and the alloy melt is sucked into the inner cavity of the copper mold by gravity. Otherwise, an appropriate level of pressure difference is added between the electric arc furnace and the copper mold atmosphere such that the alloy melt is suck into the copper mold by pressure. The copper mold has an inner cavity with a preset size of φ1 mm×32 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 1 mm and a length of 30 mm.

Exemplary 19: Zr₅₆Ti₄Cu₂₈Al₁₂ Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 20 g master alloy ingot in a quartz tube which has a nozzle with a diameter of 0.5 at a bottom end of the quartz tube. The quartz tube with the master alloy ingot is placed inside an induction coil of the induction melting unit. A copper mold which has an inner cavity with a preset of φ8 mm×100 mm is placed right below the bottom of the quartz tube. The induction melting unit, through suction provided by a mechanical pump and a diffuse pump, is set to vacuum level at 10−3 Pa. Then, highly purified hydrogen gas at 0.03 MPa is injected into the induction melting unit. The master alloy ingot is heated inside the induction coil until the master alloy ingot is completely melted into an alloy melt. Highly purified hydrogen gas is injected into the quartz tube at a top end thereof such that the alloy melt is injected into the inner cavity of the copper mold (other dimension with different diameter and length or various geometry can also be selected) at the bottom portion of the quartz tube. After cooling, the alloy melt forms an amorphous material of alloy rod which has a size of φ8 mm×40 mm.

Exemplary Embodiment 20: Zr_(49.6)Ti_(4.3)Cu₃₂Al₁₃Nb₁₁ Alloy

The starting materials are pure Zr, Ti, Cu, Al, Nb in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quinary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 0.5 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, promptly increasing a current such that the viscosity of the alloy melt is decreased and the alloy melt is sucked into the inner cavity of the copper mold by gravity. Otherwise, an appropriate level of pressure difference is added between the electric arc furnace and the copper mold atmosphere such that the alloy melt is suck into the copper mold by pressure. The copper mold has an inner cavity with a preset size of φ1 mm×32 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 1 mm and a length of 30 mm.

Exemplary Embodiment 21: Zr_(57.87)Ti_(4.13)Cu₂₈Al₁₀ Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 40 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, turning the copper crucible to pour the alloy melt to a copper mold for casting. The copper mold has an inner cavity with a preset size of φ8 mm×110 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 8 mm and a length of 70 mm.

Exemplary Embodiment 22: Zr_(63.8)Ti_(2.2)Cu₂₂Al₁₂ Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 2.0 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, promptly increasing a current such that the viscosity of the alloy melt is decreased and the alloy melt is sucked into the inner cavity of the copper mold by gravity. Otherwise, an appropriate level of pressure difference is added between the electric arc furnace and the copper mold atmosphere such that the alloy melt is suck into the copper mold by pressure. The copper mold has an inner cavity with a preset size of φ3 mm×32 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 3 mm and a length of 30 mm.

Exemplary Embodiment 23: Zr_(59.93)Ti_(2.07)Cu₂₈Al₁₀ Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 2.0 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, promptly increasing a current such that the viscosity of the alloy melt is decreased and the alloy melt is sucked into the inner cavity of the copper mold by gravity. Otherwise, an appropriate level of pressure difference is added between the electric arc furnace and the copper mold atmosphere such that the alloy melt is suck into the copper mold by pressure. The copper mold has an inner cavity with a preset size of φ3 mm×32 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 3 mm and a length of 30 mm.

Exemplary Embodiment 24: Zr₅₈Ti₈Cu₂₆Al₈ Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 0.5 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, promptly increasing a current such that the viscosity of the alloy melt is decreased and the alloy melt is sucked into the inner cavity of the copper mold by gravity. Otherwise, an appropriate level of pressure difference is added between the electric arc furnace and the copper mold atmosphere such that the alloy melt is suck into the copper mold by pressure. The copper mold has an inner cavity with a preset size of φ1 mm×32 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 1 mm and a length of 30 mm.

Exemplary Embodiment 25: Zr_(58.8)Ti_(4.2)Cu₂₇Al₁₀ Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 40 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, turning the copper crucible to pour the alloy melt to a copper mold for casting. The copper mold has an inner cavity with a preset size of φ8 mm×110 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 8 mm and a length of 70 mm.

Exemplary Embodiment 26: Zr_(63.47)Ti_(4.53)Cu₂₃Al₉ Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 2.0 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, promptly increasing a current such that the viscosity of the alloy melt is decreased and the alloy melt is sucked into the inner cavity of the copper mold by gravity. Otherwise, an appropriate level of pressure difference is added between the electric arc furnace and the copper mold atmosphere such that the alloy melt is suck into the copper mold by pressure. The copper mold has an inner cavity with a preset size of φ3 mm×32 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 3 mm and a length of 30 mm.

Exemplary Embodiment 27: Zr_(68.75)Ti_(0.25)Cu_(23.5)Al_(7.5) Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 0.5 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, promptly increasing a current such that the viscosity of the alloy melt is decreased and the alloy melt is sucked into the inner cavity of the copper mold by gravity. Otherwise, an appropriate level of pressure difference is added between the electric arc furnace and the copper mold atmosphere such that the alloy melt is suck into the copper mold by pressure. The copper mold has an inner cavity with a preset size of φ1 mm×32 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 1 mm and a length of 30 mm.

Exemplary Embodiment 28: Zr_(61.6)Ti_(4.4)Cu_(26.5)Al_(7.5) Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 2.0 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, promptly increasing a current such that the viscosity of the alloy melt is decreased and the alloy melt is sucked into the inner cavity of the copper mold by gravity. Otherwise, an appropriate level of pressure difference is added between the electric arc furnace and the copper mold atmosphere such that the alloy melt is suck into the copper mold by pressure. The copper mold has an inner cavity with a preset size of φ3 mm×32 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 3 mm and a length of 30 mm.

Exemplary Embodiment 29: Zr_(61.87)Ti_(2.13)Cu₂₄Al₁₂ Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 40 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, turning the copper crucible to pour the alloy melt to a copper mold for casting. The copper mold has an inner cavity with a preset size of φ8 mm×110 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 8 mm and a length of 70 mm.

Exemplary Embodiment 30: Zr_(60.9)Ti_(2.1)Cu₂₆Al₁₁ Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 3.5 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, promptly increasing a current such that the viscosity of the alloy melt is decreased and the alloy melt is sucked into the inner cavity of the copper mold by gravity. Otherwise, an appropriate level of pressure difference is added between the electric arc furnace and the copper mold atmosphere such that the alloy melt is suck into the copper mold by pressure. The copper mold has an inner cavity with a preset size of φ4 mm×32 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 4 mm and a length of 30 mm.

Exemplary Embodiment 31: Zr_(46.6)Ti₄Cu₃₀Al₁₅Hf_(4.4) Alloy

The starting materials are pure Zr, Ti, Cu, Al, Hf in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quinary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 0.5 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, promptly increasing a current such that the viscosity of the alloy melt is decreased and the alloy melt is sucked into the inner cavity of the copper mold by gravity. Otherwise, an appropriate level of pressure difference is added between the electric arc furnace and the copper mold atmosphere such that the alloy melt is suck into the copper mold by pressure. The copper mold has an inner cavity with a preset size of φ1 mm×32 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 1 mm and a length of 30 mm.

Exemplary Embodiment 32: Zr_(63.8)Ti_(2.2)Cu₂₃Al₁₁ Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 3.5 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, promptly increasing a current such that the viscosity of the alloy melt is decreased and the alloy melt is sucked into the inner cavity of the copper mold by gravity. Otherwise, an appropriate level of pressure difference is added between the electric arc furnace and the copper mold atmosphere such that the alloy melt is suck into the copper mold by pressure. The copper mold has an inner cavity with a preset size of φ4 mm×32 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 4 mm and a length of 30 mm.

Exemplary Embodiment 33: Zr_(62.2)Ti_(5.4)Cu_(23.5)Al_(7.5)Nb_(1.4) Alloy

The starting materials are pure Zr, Ti, Cu, Al, Nb in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quinary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 2.0 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, promptly increasing a current such that the viscosity of the alloy melt is decreased and the alloy melt is sucked into the inner cavity of the copper mold by gravity. Otherwise, an appropriate level of pressure difference is added between the electric arc furnace and the copper mold atmosphere such that the alloy melt is suck into the copper mold by pressure. The copper mold has an inner cavity with a preset size of φ3 mm×32 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 3 mm and a length of 30 mm.

Exemplary Embodiment 34: Zr_(61.87)Ti_(2.13)Cu₂₂Al₁₄ Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 25 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, turning the copper crucible to pour the alloy melt to a copper mold for casting. The copper mold has an inner cavity with a preset size of φ6 mm×110 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 6 mm and a length of 70 mm.

Exemplary Embodiment 35: Zr_(62.2)Ti_(5.4)Hf_(1.4)Cu₂₁Al₁₀ Alloy

The starting materials are pure Zr, Ti, Cu, Al, Hf in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quinary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 4 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, promptly increasing a current such that the viscosity of the alloy melt is decreased and the alloy melt is sucked into the inner cavity of the copper mold by gravity. Otherwise, an appropriate level of pressure difference is added between the electric arc furnace and the copper mold atmosphere such that the alloy melt is suck into the copper mold by pressure. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, turning the copper crucible to pour the alloy melt to a copper mold for casting. The copper mold has an inner cavity with a preset size of φ4 mm×32 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 4 mm and a length of 30 mm.

Exemplary Embodiment 36: Zr_(58.46)Ti_(1.02)Hf_(3.52)Cu₂₅Al ₁₂ Alloy

The starting materials are pure Zr, Ti, Cu, Al, Hf in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quinary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 40 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, turning the copper crucible to pour the alloy melt to a copper mold for casting. The copper mold has an inner cavity with a preset size of φ8 mm×110 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 8 mm and a length of 70 mm.

Exemplary Embodiment 37: Zr_(64.77)Ti_(2.23)Cu₂₃Al₁₀ Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 4 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, promptly increasing a current such that the viscosity of the alloy melt is decreased and the alloy melt is sucked into the inner cavity of the copper mold by gravity. Otherwise, an appropriate level of pressure difference is added between the electric arc furnace and the copper mold atmosphere such that the alloy melt is suck into the copper mold by pressure. The copper mold has an inner cavity with a preset size of φ4 mm×32 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 4 mm and a length of 30 mm.

Exemplary Embodiment 38: Zr_(67.67)Ti_(2.33)Cu₂₀Al₁₀ Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 1.5 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, promptly increasing a current such that the viscosity of the alloy melt is decreased and the alloy melt is sucked into the inner cavity of the copper mold by gravity. Otherwise, an appropriate level of pressure difference is added between the electric arc furnace and the copper mold atmosphere such that the alloy melt is suck into the copper mold by pressure. The copper mold has an inner cavity with a preset size of φ2 mm×32 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 2 mm and a length of 30 mm.

Exemplary Embodiment 39: Zr_(59.73)Ti_(4.27)Cu₂₆Al₁₀ Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 40 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, turning the copper crucible to pour the alloy melt to a copper mold for casting. The copper mold has an inner cavity with a preset size of φ8 mm×110 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 8 mm and a length of 70 mm.

Exemplary Embodiment 40: Zr_(63.47)Ti_(4.53)Cu₂₄Al₈ Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quaternary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 1.5 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, promptly increasing a current such that the viscosity of the alloy melt is decreased and the alloy melt is sucked into the inner cavity of the copper mold by gravity. Otherwise, an appropriate level of pressure difference is added between the electric arc furnace and the copper mold atmosphere such that the alloy melt is suck into the copper mold by pressure. The copper mold has an inner cavity with a preset size of φ2 mm×32 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 2 mm and a length of 30 mm.

Exemplary Embodiment 41: Zr_(59.68)Ti_(2.06)Nb_(1.26)Cu₂₈Al₉ Alloy

The starting materials are pure Zr, Ti, Cu, Al in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quinary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 4 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, promptly increasing a current such that the viscosity of the alloy melt is decreased and the alloy melt is sucked into the inner cavity of the copper mold by gravity. Otherwise, an appropriate level of pressure difference is added between the electric arc furnace and the copper mold atmosphere such that the alloy melt is suck into the copper mold by pressure. The copper mold has an inner cavity with a preset size of φ4 mm×32 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 4 mm and a length of 30 mm.

Exemplary Embodiment 42: Zr_(58.46)Ti_(2.02)Hf_(2.52)Cu₂₇Al₁₀ Alloy

The starting materials are pure Zr, Ti, Cu, Al, Hf in the forms of rod, bulk, ingot, sheet brought in the market (the purity is higher than 99.5% in percentage weight), which are processed under Ti-gettered argon atmosphere in a water-cooled copper hearth by arc melting to form a quinary master alloy ingot. The master alloy ingot is melted for several times in order to ensure compositional homogeneity. Place 40 g master alloy ingot in a water-cooled copper crucible. Arc melting the ingot to a temperature which is higher than the melting point for forming an alloy melt. After melting, turning the copper crucible to pour the alloy melt to a copper mold for casting. The copper mold has an inner cavity with a preset size of φ8 mm×110 mm (other dimension with different diameter and length or various geometry can also be selected). After cooling, the alloy melt forms an alloy rod with a diameter of 8 mm and a length of 70 mm.

One skilled in the art will understand that the embodiment of the present invention as shown in the drawings and described above is exemplary only and not intended to be limiting.

It will thus be seen that the objects of the present invention have been fully and effectively accomplished. It embodiments have been shown and described for the purposes of illustrating the functional and structural principles of the present invention and is subject to change without departure from such principles. Therefore, this invention includes all modifications encompassed within the spirit and scope of the following claims. 

1. An amorphous Nickel-Free Zirconium alloy which is readily formed through copper mold casting, comprising a composition consisting of a first to fourth elements in which the first element is zirconium (Zr), the second element is titanium (Ti), the third element is copper (Cu) and the fourth element is aluminum (Al), wherein an atomic percent of the first to the fourth elements in the composition are represented by a, b, c and d respectively, wherein a=45˜69%, b=0.25˜8%, c=21˜35%, and d=7.5˜15%, where a sum of a, b, c and d is smaller than or equal to 100%.
 2. An amorphous Nickel-Free Zirconium alloy, as recited in claim 1, wherein said composition has a chemical formula of Zr_(a)Ti_(b)Cu_(c)Al_(d) in which a+b has a range of 55˜69%.
 3. An amorphous Nickel-Free Zirconium alloy, as recited in claim 2, wherein an atomic percentage of zirconium (Zr) relative to titanium (Ti) is 92˜99.5%, wherein an atomic percentage of titanium (Ti) relative to zirconium (Zr) is 0.5˜8%.
 4. An amorphous Nickel-Free Zirconium alloy, as recited in claim 3, wherein in said chemical formula, a+b has a range of 55˜69% in atomic percent, and said fourth element aluminum (Al) has a range of 8˜13% in atomic percent.
 5. An amorphous Nickel-Free Zirconium alloy, as recited in claim 1, wherein said composition further consists of a fifth element hafnium (Hf) and has a chemical formula of Zr_(a)Hf_(e)Ti_(b)Cu_(c)Al_(d), where a, b, c, d, e are atomic percent of the first to fifth elements respectively, wherein a=45˜69%, b=0.25˜8%, c=21˜35%, d=7.5˜15%, b+e=0.25˜15%, where a sum of a, b, c, d and e is equal to 100%.
 6. An amorphous Nickel-Free Zirconium alloy, as recited in claim 5, wherein in said chemical formula of said composition Zr_(a)Hf_(e)Ti_(b)Cu_(c)Al_(d), a+b+e has a range of 55˜69%.
 7. An amorphous Nickel-Free Zirconium alloy, as recited in claim 6, wherein an atomic percentage of zirconium (Zr) relative to titanium (Ti) is 92˜99.5%, wherein an atomic percentage of titanium (Ti) relative to zirconium (Zr) is 0.5˜8%.
 8. An amorphous Nickel-Free Zirconium alloy, as recited in claim 1, wherein said composition further consists of an additional element niobium (Nb) and has a chemical formula of Zr_(a)Nb_(f)Ti_(b)Cu_(c)Al_(d), where a, b, c, d, f are atomic percents of the first to fourth elements and the additional element respectively, wherein a=45˜69%, b=0.25˜8%, c=21˜35%, d=7.5˜13%, b+f=0.25˜10%, where a sum of a, b, c, d and f is equal to 100%.
 9. An amorphous Nickel-Free Zirconium alloy, as recited in claim 8, wherein in said chemical formula of said composition Zr_(a)Nb_(f)Ti_(b)Cu_(c)Al_(d), a+b+f has a range of 55˜69%.
 10. An amorphous Nickel-Free Zirconium alloy, as recited in claim 9, wherein an atomic percentage of zirconium (Zr) relative to titanium (Ti) is 92˜99.5%, wherein an atomic percentage of titanium (Ti) relative to zirconium (Zr) is 0.5˜8%. 